Palladium catalyst, method for its preparation and its use

ABSTRACT

The invention relates to palladium(0)-tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine} complex of formula (I), as well as to its preparation and use. 
     
       
         
         
             
             
         
       
     
     This compound is outstandingly stable, and can be used as catalyst with excellent results.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of International PatentApplication No. PCT/HU2011/000122, filed Dec. 13, 2011, which claimspriority to Hungary patent application No. P-1000668, filed Dec. 16,2010. The disclosures of the related applications are incorporated byreference herein in their entireties.

TECHNICAL FIELD

The invention relates to a new palladium catalyst, more particularly topalladium(0)-tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine}complex of formula (I)

[empirical formula: Pd{[3,5-(CF₃)₂—C₆H₃]₃P}₃].

The invention relates further to a method for the preparation of the newcatalyst. The invention also relates to the use of the new catalyst inreactions requiring such catalysts, more particularly in reactions toform a C—C bond (cross coupling reactions, such as Suzuki, Heck, Stilleetc. couplings), in reaction to form a C-heteroatom (C—N, C—O, C—S, C—P,primarily C—N) bond (e.g. Buchwald reaction), and for hydrogenationreactions.

As nowadays cross coupling reactions catalysed by complexes oftransition metals (most frequently by Pd and Ni complexes) have anoutstanding role in the formation of a C—C bond, and such reactions havebrought about radical changes in synthesis routes, the invention will bediscussed in the following primarily in connection with cross couplingreactions without, however, restricting its scope to this mode of use.

BACKGROUND

The gross process of cross coupling reactions can be described as

whereinR and R′ represent organic groups to be coupled with a C—C bond,M is the metal component of the catalyst complex,L represents the ligands present in the catalyst complex,n is the number of ligands present,X is a leaving atom or group (e.g. Cl, Br, I, triflate, mesylate,tosylate), andM′ is a metal or metal-containing group corresponding to the type of thecross coupling reaction concerned (e.g. this metal component is boronfor Suzuki-Miyaura coupling, copper for Sonogashira coupling, magnesiumfor Kharash coupling, silicon for Hiyama coupling, tin for Stillecoupling, zinc for Negishi coupling, etc.).

The general mechanism of cross coupling reactions is shown below.

However, from the aspects of practical utilization these methods havesome disadvantages, which are particularly pronounced in the field ofpharmaceutical industry. One of them is that rather high amounts ofcatalyst (1-5 mol % related to the substrate) are required, furthermoremetal impurities originating from the catalyst can be removed from theend product generally only by tedious and expensive operations. Thislatter is particularly valid for palladium catalysts, which, inaddition, are highly liable to decomposition. As an example, whenpalladium(0)-tetrakis(tri-phenyl-phosphine) of formula (II),

which is still an industrially frequently used catalyst, is stored inair at room temperature, a considerable amount of palladium blackseparates within a short time, thus it is advisable to store it in arefrigerator under argon atmosphere. Although cross coupling reactionsutilizing the catalyst of formula (II) are performed under inertatmosphere, separation of palladium black is still common, which causesnot only a considerable loss in catalyst, but tedious time-consuming andexpensive purification steps should also be introduced.

DESCRIPTION

The aim of the invention was to provide a new palladium(0) complexcatalyst which is much more stable than the palladium(0) complexcatalysts used before in cross coupling reactions, and also enables oneto considerably reduce the amount of catalyst required for 1 mole ofsubstrate. Within this domain our primary aim was to eliminate palladiumblack formation, as palladium black formed from Pd(0) complexes is afinal state, which catalyst decomposition markedly reduces the overallcatalytic efficiency. Additionally, the uncontrolled decomposition ofthe catalyst often results in intolerable amounts of P being leachedinto the product.

Now we have found that the palladium(0) complex catalyst of formula (I)fully satisfies the above requirements and has further advantages, too.

Thus, in one aspect, the present invention relates to the palladium(0)complex of formula (I).

This compound is a bright lemon yellow colored solid with outstandingstability: no formation of palladium black could be observed even insamples stored in air at room temperature for more than 20 months.

The compound of formula (I) was stored in air at varying T temperaturesand humidities. Samples were taken periodically from the stored product,and the decomposition of the product was examined on the basis of ³¹P,¹⁹F, ¹³C and ¹H NMR spectra. The results are summarized in the followingtable.

Period (month) T, ° C. Humidity, % Colour and grade of decomposition ofthe stored product 1 5 Gradually Lemon yellow; no sampling was madechanging 25 60 Lemon yellow; no decomposition was shown by NMR 30 65Lemon yellow; no decomposition was shown by NMR 40 75 Lemon yellow; nodecomposition was shown by NMR 4 5 Gradually Lemon yellow; no samplingwas made changing 25 60 Lemon yellow; no decomposition was shown by NMR30 65 Lemon yellow; no decomposition was shown by NMR 40 75 Lemonyellow; no decomposition was shown by NMR 7 5 Gradually Lemon yellow; nosampling was made changing 25 60 Lemon yellow; no decomposition wasshown by NMR 30 65 Lemon yellow; no decomposition was shown by NMR 40 75Lemon yellow; no decomposition was shown by NMR 13 5 Gradually Lemonyellow; no sampling was made changing 25 60 Lemon yellow; nodecomposition was shown by NMR 30 65 Lemon yellow; no decomposition wasshown by NMR 40 75 Lemon yellow; no decomposition was shown by NMR 20 5Gradually Lemon yellow; no sampling was made changing 25 60 Lemonyellow; no decomposition was shown by NMR 30 65 Lemon yellow; nodecomposition was shown by NMR 40 75 Lemon yellow; no decomposition wasshown by NMR

When examining the compound of formula (I) by DSC, decomposition wasobserved at 169.5° C. in air under atmospheric pressure. When performingthe test in inert atmosphere the melting point of the compound was foundto be 220° C. Just for the comparison, the non-fluorinated catalyst offormula (II) started to decompose at 98° C.

When examining the possible reasons for the outstanding storagestability of the compound of formula (I) compared to that of its closestructural analogue of formula (II), which is widely used in theindustry, DFT calculations were performed to determine the metal-ligandbinding energies. On B3LYP/lanl2dz level the following measurements wereobtained:

L = P(C₆H₅)₃ [formula L = P[C₆H₃(CF₃)₂]₃ (II)] [formula (I)] PdL → Pd +L −40.1 kcal/mol −39.5 kcal/mol PdL₂ → PdL + L −38.0 kcal/mol −42.3kcal/mol PdL₃ → PdL₂ + L −27.9 kcal/mol −45.6 kcal/mol

According to this calculation for compounds comprising three ligands(i.e. of real structures) the metal-ligand binding energy in thecompound of formula (I) is about the twofold of that observed for thecompound of formula (II). On this basis we assume that the outstandingstorage stability of the compound of formula (I) cannot be attributed toa metal-ligand interaction, but to specific ligand-ligandinter-actions(s).

Stability tests were performed on Pd(0)-tris[tri-(substitutedphenyl)-phosphine] complex catalysts where two of the three3,5-(trifluoromethyl)-phenyl groups attached to the phosphorous atom inthe ligand were retained, but the third one was replaced by mono-, di-or trimethoxy-phenyl, tri-isopropyl-phenyl or 2-pyridyl group. None ofthese compounds could even approximate the compound of formula (I) instorage stability. Thus the outstanding storage stability of thecompound of formula (I) is a very surprising characteristic, which doesnot appear even with its very close structural analogues.

When examining the stability of the catalyst of formula (I) in crosscoupling reaction conditions we have found that the catalyst is notsensitive to temperature rise; it retains its stability at anytemperature below its melting point. Similarly, an increase in pressurehad no influence on the stability of the catalyst.

When examining the stability of the catalyst of formula (I) thefollowing properties have been found:

The catalyst is not soluble in water at industrially relevanttemperatures; simultaneously it remains unrestrictedly stable whenstored in water.

The solubility of the catalyst in alcohols at room temperature increaseswith the increase of the carbon atom numbers of the alcohol; however, atthe tested temperature intervals of catalytic reactions (110-130° C.)its stability in alcohols decreases in parallel with the increase of thecarbon atom numbers of the alcohol. However, the stability of thecatalyst can be increased or even completely restored when adding waterto the reaction mixture. In aqueous alcohols the dissolution of thecatalyst starts at around 90° C. and, depending on the alcoholconcerned, it is complete at 110-130° C., where the catalytic activityreaches its maximum. However, even at temperatures leading to completedissolution no separation of palladium black was observed. Sometimesthere occurred a minor tolerable decomposition, which was shown by aslight deepening of the colour of the reaction mixture (from lemonyellow to yellowish brown). It is particularly remarkable that evenunder such conditions full (100%) conversion could be attained. As acomparison: when the compound of formula (II) was used as catalyst undermuch milder conditions than those discussed above (atmospheric pressure;boiling point of the reaction mixture) the formation of palladium blackcould not be avoided, which clearly indicates a considerabledecomposition of the catalyst.

In order to avoid the use of superatmospheric pressures, which isundesirable from industrial aspects, the stability of the catalyst offormula (I) was also tested in industrially important polar aprotic andapolar aprotic organic solvents (e.g. dimethyl sulphoxide, dimethylformamide, ethyl-methyl-ketone, methyl-isobutyl-ketone,N-methyl-pyrrolidine and tetrahydrofuran) in which the catalyst fullydissolves at lower temperatures. No formation of palladium black wasobserved in these solvents, either, although sometimes the color of thereaction mixture got deeper to some extent during the catalytic reaction(discoloration from lemon yellow to pink, orange, red or brownish wereobserved). Like with the alcohols discussed above, in some of thesesolvents the slight stability decrease of the catalyst can be suppressedconsiderably by adding water to the reaction mixture.

When examining the catalytic activity of the compound of formula (I) incross coupling reactions we have found that on the same substrate andunder otherwise identical reaction conditions the required amount of thenew catalyst can be lowered to a fragment of the amount of similar knowncatalysts (from 1-5 mole % related to the substrate to 0.1-0.3 mole %related to the substrate) without any remarkable decrease in yield andconversion attained under the same reaction time. Although the yield andconversion attained under the same reaction conditions under a givenreaction time decreases when the amount of catalyst is further loweredbelow this level, this can be well counterbalanced by increasing thetemperature and/or time of the reaction. As an example: in a Suzukicoupling of 2-bromo-pyridine with2-(4-ethoxy-3-methyl-phenyl)-1,3,2-dioxaborolane performed in a 10:1 v/vmixture of methanol and water in the presence of K₂CO₃ at 110° C. underpressure 100% conversion was attained within 1 hour when using 0.25 mole% of the catalyst of formula (I). When lowering the amount of thecatalyst to 0.05 mole % (which is 20% of the former value) theconversion attained within 1 hour still remained rather high (81%), andwhen using only 0.005 mole % of the catalyst (which is 2% of the formervalue and 1-5 thousandth of the usual industrial values) a conversion of50% could even be attained within 1 hour.

In most instances it is not required to remove palladium from theproduct, because, owing to the low amount and high stability of the newcatalyst, no palladium remains in the product, or the amount of residualpalladium is below the acceptable level. Should residual palladium stillbe removed, the expensive scavenger methods [specific operations forbinding Pd(0)] routinely used for this purpose can be fully omitted. Theresidual, still complexed palladium can be removed by simple operations(chromatography; filtration through an inexpensive carbon filter, etc.)routinely used in industry, and usually no more than one purificationstep is required.

The invention relates further to a method for preparing the compound offormula (I).

The catalyst of formula (I) can be readily prepared by reacting apalladium(II) salt with at least fourfold molar excess oftri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine and reducingpalladium(II) to palladium(0) in the resulting complex salt in a one-potreaction. As palladium(II) salt preferably palladium dichloride can beused; a preferred reducing agent is hydrazine hydrate.

Tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine used as complexing agentis a known substance [see e.g. H. G. Alt, R. Baumgaertner, H. A. Brune:Chemische Berichte 119(5), 1694-1703 (1986)].

The invention also relates to the use of the compound of formula (I) ascatalyst in C—C and C-heteroatom coupling reactions as well as forhydrogenation. We have found that the compound of formula (I) can beused in any type of these reactions. The conditions of such reactionsmay be the same as applied when using other Pd(0) complex catalysts,with the difference that when using the compound of formula (I) ascatalyst usually lower, sometimes much lower amounts of catalyst arestill sufficient to perform the reaction. Based on this generalknowledge and on the information presented in this description, oneskilled in the art can easily determine optimum parameters for reactionsutilizing the catalyst of formula (I), by applying routine methods orsometimes simple tests and taking into account the dissolutioncharacteristics of the catalyst. It should be noted here that the ideausing the in situ prepared catalyst of formula (I) (for examplePd₂(dba)₃ with PPh₃(CF₃)₆) is not viable, because of the uncontrolledformation of the complex and of the almost immediate appearance ofPd-black results in poor yields.

The following Examples serve to illustrate further details of theinvention.

Example 1 Preparation of the Catalyst of Formula (I)

Argon was bubbled through 30 ml of dimethyl sulphoxide at roomtemperature, and then 6.7 g (0.01 mole) oftri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine and 0.355 g (0.002 mole)of palladium(II) chloride were added. Thereafter the mixture was heatedto 110-130° C. When a fully clear solution was obtained, indicating thata complex was formed, 0.5 g (0.01 mole) of hydrazine hydrate was addedto the mixture. Thereafter the flask was immersed into ice water. Theseparated product was filtered through a sintered glass filter andwashed three times with chloroform. A bright lemon yellow colouredcrystalline solid was obtained with a yield of 90%.

Characteristic data of NMR spectra: ¹H-NMR (300 MHz, THF-d₈, δ=3.58 ppm)8.17 (s, 12H), 7.84 (s, 24H); ¹³C-NMR (75 MHz, THF-d₈, δ=67.3 ppm) 138.1(C), 133.7 (q, J=38.7 Hz, C), 133.4 (CH), 126.3 (CH), 123.4 (q, J=271.57Hz, CF₃); ³¹P-NMR (300 MHz, THF-d₈) 28.77; ¹⁹F-NMR (300 MHz,THF-d₈)-62.94.

Example 2 Preparation of 2-(4-ethoxy-3-methyl-phenyl)-pyridine by SuzukiCoupling Using a 10/1 v/v Mixture of Methanol and Water as Solvent andthe Compound of Formula (I) as Catalyst

General Prescription:

An amount of the catalyst of formula (I) to be given below, 618 mg (3mmoles) of 2-(4-ethoxy-3-methyl-phenyl)-1,3,2-dioxaborolane and 553 mg(4 mmoles) of potassium carbonate were weighed into a flask. Thereafterthe flask was placed under argon atmosphere, and 10 ml of methanol and 1ml of water were added. Finally 316 mg (190 μl, 2 mmoles) of2-bromo-pyridine (substrate) were introduced with an automatic pipette.The flask was closed, and the reaction mixture was stirred at atemperature and for a time to be given below, optionally undersuperatmospheric pressure.

For processing purposes, the cooled reaction mixture was extracted fourtimes with 5 ml of chloroform, each; in this way almost the full amountof catalyst was removed from the product. As the chloroform extractstill contained dioxoborolane impurity, the thus separated substance wasfurther purified by silica gel column chromatography, utilizing a 3/1v/v mixture of hexane and ethyl acetate as eluting agent.

Test Series (A):

In this test series the reactions were performed at 110° C. temperatureand under superatmospheric pressure for 1 hour. The amount of thecompound of formula (I) was varied, and it was examined how thisvariation influences the conversion attained.

In all of the cases presented in this description conversion values weredetermined on the basis of ¹H NMR spectra or by gas chromatography. Theresults are summarized in Table 1. Although with these rather smallscale test reactions the processing of the mixture influences theisolated yield, these data are also given for information purposes.

TABLE 1 Amount of the catalyst Conversion attained Isolated mg mole %related to the substrate within 1 hour yield, % 56 1 100 89 28 0.5 10087 14 0.25 100 88 2.8* 0.05 81 69 0.28* 0.005 50 39 *The catalyst wasadded to the mixture as a stock solution formed with tetrahydrofuran.

No separation of palladium black was observed in any of the cases; thecolour of the reaction mixture remained lemon yellow in all of thereactions. It is particularly remarkable that a 50% conversion couldstill be attained within 1 hour when the amount of the catalyst offormula (I) was as low as 0.005 mole %. According to our experiencesgathered in other tests this decrease in conversion can becounterbalanced by increasing the time and/or the temperature of thereaction.

In tests performed for checking purposes the above reaction was repeatedso that no catalyst was added to the reaction mixture. In this way weintended to ascertain that the formation of the product can indeed beattributed to the catalyst administered in a very low amount, and not tothe effect of any metal impurities which might be present in thesolvents or in the flasks. Under these conditions the conversion waszero, thus it can be stated with full certainty that the catalyst offormula (I) is active even in an amount of 0.005 mole %.

Test Series (B):

In this test series 0.25 mole % of the catalyst of formula (I) was usedfor 1 mole of 2-bromo-pyridine substrate, and the reactions wereperformed for 1 hour at temperatures listed in Table 2, undersuperatmospheric pressure if required. It was examined how the changesin temperature influence the conversion attained. The results are listedin Table 2; the isolated yields are also given for information purposes.

TABLE 2 Isolated yield, Temperature, ° C. Conversion attained within 1hour, % % 25 0  0 50 5 not measured 70 25 16 90 60 47 110 100 88

The observed results show that when using a 10/1 v/v mixture of methanoland water as reaction medium, it is advisable to perform the couplingreaction at temperatures above 90° C. and under superatmosphericpressures which enable the reaction mixture to remain liquid. This canbe explained by the fact that a remarkable dissolution of the catalystoccurs at such temperatures. Formation of palladium black or any othersign of catalyst decomposition could not be observed in any of thereactions. As a comparison: when in the reaction performed at 110° C.the catalyst of formula (I) was replaced by the same amount of thecatalyst of formula (II), the reaction mixture got black within someminutes. After terminating the reaction it is very difficult to removemetal impurities. The product obtained in this latter reaction remainedorange yellow/dark orange yellow even after full removal of palladiumblack, whereas when using the catalyst according to the invention snowwhite product was obtained.

The physical constants of all of the product samples obtained in Example2 were, within the limits of measurement accuracy, in good agreementwith one another and with the respective parameters of the authenticproduct sample. For information purposes we present below the physicalconstants measured by us on a 2-(4-ethoxy-3-methoxy-phenyl)-pyridinesample prepared in a 10/1 v/v mixture of methanol and water at 110° C.for 1 hour utilizing 0.25 mole % of the catalyst of formula (I):

¹H NMR (300 MHz, CDCl₃, δ_(TMS)=0 ppm): 8.65 (d, J=4.8 Hz, 1H), 7.75 (m,4H), 7.16 (m, 1H), 6.90 (d, J=8.4 Hz, 1H), 4.10 (q, J=6.9 Hz, 2H), 2.31(s, 3H), 1.45 (t, J=7.2 Hz).

¹³C-NMR (75 MHz, CDCl₃, δ_(CDCl3)=77.00 ppm): 158.2 (C), 157.3 (C),149.3 (CH), 136.7 (CH), 131.1 (C), 129 (CH), 127.1 (C), 125.5 (CH),121.2 (CH), 119.9 (CH), 111.0 (CH), 63.6 (CH₂), 16.4 (CH₃), 14.9 (CH₃).

IR (KBr, ν cm⁻¹): 1604, 1587, 1561, 1467, 1433, 1394, 1309, 1281, 1247,1181, 1151, 1131, 1109, 1042, 926, 884, 777, 742, 618.

Example 3 Preparation of 2-(4-ethoxy-3-methyl-phenyl)-pyridine by SuzukiCoupling in Reaction Media Other than a 10/1 v/v Mixture of Methanol andWater and Using the Compound of Formula (I) as Catalyst

The Suzuki coupling described in Example 2 was repeated using 316 mg(190 μl, 2 mmoles) of 2-bromo-pyridine as substrate and a total amountof 11 ml of reaction medium, however, the reaction conditions(composition of the reaction mixture; amount of the catalyst; amount ofthe dioxoborolane reagent; reaction time; temperature) were varied asindicated in Table 3. The conversion was measured as described inExample 2. The results are listed in Table 3.

TABLE 3 Dioxo boro- Solvent Catalyst Time lane, Temperature Conversion10 ml/1 ml mg/mole % hour equiv. ° C. % EtOH/H₂O 14/0.25 1 1.5 110 100iPrOH/H₂O 14/0.25 1 1.5 110 100 tBuOH/H₂O 14/0.25 1 1.5 110 100Hexan/H₂O 14/0.25 1 1.5 110 27 DME/H₂O 14/0.25 1 1.5 110 48 THF/H₂O14/0.25 1 1.5 110 85 THF/H₂O 0.112/0.002 19 1.5 110 26 THF/H₂O0.112/0.002 72 1.5 110 78 THF/H₂O 0.112/0.002 1 1.5 130 39 THF/H₂O0.112/0.002 3 1.5 130 74 THF/H₂O 0.112/0.002 19 1.5 130 100 THF/H₂O0.112/0.002 3 1.1 130 33

When aqueous ethanol, aqueous isopropanol and aqueous tert.butanol wereused, during the reaction time of 1 hour the colour of the reactionmixture gradually deepened and got brown; the order of deepening orderwas ethanol-isopropanol-tert.butanol. However, no palladium blackseparated in any of the instances, and the conversion remained 100%,reflecting that the catalyst retained its activity. When conducting thereaction in hexane/water, dimethoxyethane/water andtetrahydro-furan/water mixtures we have found that the quality of theorganic solvent component of the reaction mixture highly influences theconversion attainable within a given period of time. This is a usualphenomenon with cross coupling reactions. Again, no formation ofpalladium black could be observed with these solvents, althoughsometimes the colour of the reaction mixture deepened during thereaction. The results of the tests performed in tetrahydrofuran/watermixture are particularly remarkable. The test was also done with anextremely low amount of catalyst (0.002 mole %; about one thousandth ofthe amount required from known catalysts). Like in Example 2, thisextremely low amount of catalyst was introduced into the mixture as astock solution in tetrahydrofuran. The data clearly indicate that thedecrease in conversion can be well counterbalanced by increasing thereaction time and/or the reaction temperature: upon raising thetemperature to 130° C. and the reaction time to 19 hours 100% conversioncould be attained even with this extremely low amount of catalyst. Uponperforming the checking test described in Example 2 (reaction withoutcatalyst) we have ascertained again that product formation can beattributed solely to the presence of the catalyst, and not to the effectof any possible metal impurities which might be present in the solventsor in the flasks. The outstanding stability of the catalyst of formula(I) is well illustrated by the fact that no sign of catalystdecomposition could be observed even after a reaction performed at 130°C. for 19 hours, which is a very drastic condition.

Example 4 Preparation of Pyridine Derivatives by Suzuki Coupling, Usingthe Catalyst of Formula (I)

General Prescription:

14 mg (0.25 mole % related to the 2-bromo-pyridine substrate) of thecatalyst of formula (I), 3 mmoles of the dioxaborolane reagent and 553mg (4 mmoles) of potassium carbonate were weighed into a flask.Thereafter the flask was placed under argon atmosphere, and 10 ml ofmethanol and 1 ml of water were added. Finally 316 mg (190 μl, 2 mmoles)of 2-bromo-pyridine (substrate) were introduced with an automaticpipette. The flask was then closed, and the reaction mixture was stirredfor 1 hour at 110° C. under a pressure required to maintain a liquidreaction mixture. Thereafter the reaction mixture was processed asdescribed in Example 2.

The reactants used, the products obtained and their physical constants,as well as the isolated yields (%) are listed in Table 4.

TABLE 4 Product Reactant ¹H-NMR (300 MHz, CDCl₃) Yield, %2-(4-Methoxy-3- 2-(4-Methoxy-3- 8.65 (d, J = 4.5 Hz, 1H), 7.80 (m, 73methyl-phenyl)- methyl-pheny)- 7.70 (m, 2H), 7.14 (m, 1H), pyridine1,2,3-dioxaborolane 6.91 (d, J = 8.1 Hz, 1H), 3.88 (s, 3H). 2.30 (s, 3H)2-(3,4-Dimethoxy- 2-(3,4-Dimethoxy- 8.65 (d, J = 4.5 Hz, 1H), 7.69 (m,75 phenyl)-pyridine phenyl)-boronic 3H), 7.5 (d, J = 8.1 Hz, 1H), acid7.18 (m, 1H), 6.59 (d, J = 8.1 Hz, 1H), 3.99 (s, 3H) 2-(4-Methoxy-2-(4-Methoxy- 8.65 (d, J = 4.8 Hz, 1H), 7.94 (d, 58 phenyl)-pyridinephenyl)-1,3,2-dioxaborolane J = 9 Hz, 2H), 7.69 (m, 2H), 7.16 (m, 1H),6.99 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H) 2-(p-Tolyl)-pyridine2-(p-Tolyl)-1,3,2-- 8.68 (d, J = 4.5 Hz, 1H), 7.90 (d, 62 dioxaborolaneJ = 8.4 Hz, 2H), 7.73 (m, 2H), 7.26 (m, 2H), 7.21 (m, 1H), 2.41 (s, 3H)2-(4-Fluoro- 2-(4-Fluoro-phenyl)- 8.67 (d, J = 4.8 Hz, 1H), 7.98 (m, 26phenyl)-pyridine 1,3,2-dioxaborolane 3H)  90* *Yield attained after 16hours of reaction

The physical constants of all of the obtained products were, within thelimits of measurement accuracy, in good agreement with the respectiveparameters of the authentic product samples. The reaction mixturesalways remained lemon yellow, even after a reaction time of 16 hours. Nosign referring to an optional decomposition of the catalyst could bedetected.

Example 5 Preparation of Indole Derivatives by Suzuki Coupling, Usingthe Catalyst of Formula (I)

General Prescription:

14 mg (0.25 mole % related to the 5-bromo-indole substrate) of thecatalyst of formula (I), 3 mmoles of the dioxaborolane reagent, 553 mg(4 mmoles) of potassium carbonate and 390 mg (2 mmoles) of5-bromo-indole were weighed into a flask. Thereafter the flask wasplaced under argon atmosphere, and 10 ml of methanol and 1 ml of waterwere added. The flask was then closed, and the reaction mixture wasstirred for 1 hour at 110° C. under a pressure required to maintain aliquid reaction mixture.

Of the end-products obtained only 5-(p-tolyl)-1H-indole is soluble inwater. When preparing this compound, the reaction mixture was processedas described in Example 2.

The reaction mixtures comprising other (water insoluble) indolecompounds were processed as follows:

9 ml of water were added to the reaction mixture, and the separatedsolid, which comprises the catalyst and the product, was filtered offthrough a sintered glass filter. In order to remove the catalyst, theresulting solid was dissolved in chloroform, the chloroform-insolublecatalyst was filtered off, the filtrate was dried over sodium sulphateand evaporated then in vacuo.

The reactants used, the products obtained and their physical constants,as well as the isolated yields (%) are listed in Table 5.

TABLE 5 Product Reactant ¹H-NMR (300 MHz, CDCl₃) Yield, % 5-(4-Ethoxy-3-2-(4-Ethoxy-3- 8.10 (bs, 1H), 7.83 (s, 1H), 93 methyl-phenyl)-methyl-phenyl)- 7.43 (m, 4H), 7.22 (m, 1H), 6.91 (d, 1H-indole1,3,2-dioxaborolane J = 8.4 Hz, 1H), 6.61 (s, 1H), 4.11 (q, J = 6.9 Hz,2H), 2.34 (s, 3H), 1.48 (t, J = 6.9 Hz, 3H) 5-(4-Methoxy-3-2-(4-Methoxy-3- 8.13 (bs, 1H), 7.82 (s, 1H), 90 methyl-phenyl)-methyl-phenyl)- 7.44 (m, 4H), 7.22 (m, 1H), 6.92 (d, 1H-indole1,3,2-dioxaborolane J = 9 Hz, 1H), 6.60 (s, 1H), 3.89 (s, 1H), 2.32 (s,3H) 5-(4-Methoxy- 2-(4-Methoxy- 8.12 (bs, 1H), 7.84 (s, 1H), 87phenyl)-1H-indole phenyl)-1,3,2-di- 7.60 (m, 2H), 7.44 (s, 2H), 7.22 (t,J = 3 Hz, oxaborolane 1H), 7.02 (m, 2H), 6.62 (t, J = 2.4 Hz, 1H), 3.83(s, 3H) 5-(3,4-Dimethoxy- 2-(3,4-Dimethoxy- 82 (bs, 1H), 7.81 (s, 1H),94 phenyl)-1H-indole phenyl)-boronic 7.42 (s, 2H), 7.21 (m, 3H), 6.95(d, J = 8.7 Hz, acid 1H), 6.59 (m, 1H), 3.96 (s, 3H), 3.92 (s, 3H)5-(p-Tolyl)-1H- 2-(p-Tolyl)-1,3,2-- 8.13 (bs, 1H), 7.87 (s, 1H), 92indole dioxaborolane 7.58 (d, J = 8.1 Hz, 2H), 7.45 (m, 2H), 7.28 (d, J= 8.4 Hz, 2H), 7.24 (m, 1H), 6.6 (m, 1H), 2.43 (s, 3H) 5-Phenyl-1H-Phenylboronic 8.12 (bs, 1H), 7.90 (s, 1H), 84 indole acid 7.70 (d, J =7.2 Hz, 2H), 7.47 (m, 4H), 7.35 (m, 1H), 7.24 (m, 1H), 6.64 (m, 1H)5-(4-Fluoro- 2-(4-Fluoro- 8.13 (bs, 1H), 7.84 (s, 1H), 77 phenyl)-1H-phenyl)-1,3,2-di- 7.62 (m, 2H), 7.43 (m, 2H), 7.24 (m, indoleoxaborolane 1H), 7.16 (m, 2H), 6.64 (m, 1H)

The physical constants of all of the obtained products were, within thelimits of measurement accuracy, in good agreement with the respectiveparameters of the authentic product samples. No appearance of palladiumblack was observed in the reaction mixtures; the separated catalystalways remained lemon yellow.

Example 6 Preparation of Isoquinoline Derivatives by Suzuki Coupling,Using the Catalyst of Formula (I)

General Prescription:

14 mg (0.25 mole % related to the 5-bromo-isoquinoline substrate) of thecatalyst of formula (I), 3 mmoles of the dioxaborolane reagent, 553 mg(4 mmoles) of potassium carbonate and 416 mg (2 mmoles) of5-bromo-isoquinoline were weighed into a flask. Thereafter the flask wasplaced under argon atmosphere, and 10 ml of methanol and 1 ml of waterwere added. The flask was then closed, and the reaction mixture wasstirred for 1 hour at 110° C. under a pressure required to maintain aliquid reaction mixture. The resulting reaction mixtures were processedas described in Example 2.

The reactants used, the products obtained and their physical constants,as well as the isolated yields (%) are listed in Table 6.

TABLE 6 Product Reactant ¹H-NMR (300 MHz, CDCl₃) Yield, % 5-(4-Ethoxy-3-2-(4-Ethoxy-3- 9.22 (s, 1H), 8.40 (d, J = 6 Hz, 1H) 89methyl-phenyl)-isoquinoline methyl-phenyl)- 7.87 (m, 1H), 7.70 (d, J = 6Hz, 1H) 1,3,2-dioxaborolane 7.50 (d, J = 6 Hz, 1H), 7.10 (d, J = 6 Hz,1H), 6.87 (d, J = 9 Hz, 1H), 4.05 (q, J = 6.9 Hz, 2H), 2.24 (s, 3H),1.41 (t, J = 6.9 Hz, 3H) 5-(4-Methoxy-3 2-(4-Methoxy-3- 9.29 (s, 1H),8.48 (d, J = 6 Hz, 1H) 85 methyl-phenyl)-isoquinoline methyl-phenyl)-7.95 (m 1H), 7.77 (d, J = 6 Hz, 1H), 1,3,2-dioxaborolane 7.60 (m, 2H),7.28 (m, 2H), 6.96 (d, J = 8.7 Hz, 1H), 3.92 (s, 3H), 2.32 (s, 3H)5-(3,4-Dimethoxy- 3,4-Dimethoxy- 9.31 (bs, 1H), 8.47 (m, 1H), 89phenyl)-isoquinoline phenyl-boronic 7.95 (m, 1H), 7.78 (d, J = 6 Hz,1H), acid 7.65 (m, 2H), 7.00 (m, 3H), 3.97 (s, 3H), 3.91 (s, 3H)5-(4-Methoxy- 2-(4-Methoxy- 9.30 (s, 1H), 8.48 (d, J = 6 Hz, 1H) 57phenyl)-isoquinoline phenyl)-1,3,2-di- 7.97 (m, 1H), 7.75 (d, J = 6 Hz, 90* oxaborolane 1H), 7.41 (s, 2H), 7.05 (m, 2H), 3.90 (s, 3H)5-(p-Tolyl)-isoquinoline 2-(p-Tolyl)-1,3,2-di- 9.31 (s, 1H), 8.48 (d, J= 6.3 Hz, 59 oxaborolane 1H), 7.98 (m, 1H), 7.75 (d, J = 6 Hz,  91* 1H),7.66 (m, 2H), 7.35 (m, 4H), 2.43 (s, 3H) 5-(4-Fluoro- 2-(4-Fluoro- 9.3(s, 1H), 8.49 (d, J = 6.3 Hz, 56 phenyl)-isoquinoline phenyl-1,3,2-di-1H), 7.97 (m, 1H), 7.62 (m, 3H), oxaborolane 7.42 (m, 2H), 7.22 (m, 2H)*Yield attained after 3 hours of reaction.

The physical constants of all of the obtained products were, within thelimits of measurement accuracy, in good agreement with the respectiveparameters of the authentic product samples. The reaction mixturesalways remained lemon yellow, and no sign referring to an optionaldecomposition of the catalyst could be detected.

Example 7 Preparation of Biphenyl Derivatives by Suzuki Coupling, Usingthe Catalyst of Formula (I)

General Prescription:

14 mg (0.25 mole % related to the p-bromo-toluene substrate) of thecatalyst of formula (I), 3 mmoles of the dioxaborolane reagent, 553 mg(4 mmoles) of potassium carbonate and 342 mg (2 mmoles) ofp-bromo-toluene were weighed into a flask. Thereafter the flask wasplaced under argon atmosphere, and 10 ml of methanol and 1 ml of waterwere added. The flask was then closed, and the reaction mixture wasstirred for 1 hour at 110° C. under a pressure required to maintain aliquid reaction mixture. The resulting reaction mixtures were processedas described in Example 5.

The reactants used, the products obtained and their physical constants,as well as the isolated yields (%) are listed in Table 7.

TABLE 7 Product Reactant ¹H-NMR (300 MHz, CDCl₃) Yield, %4-Ethoxy-3,4′-di- 2-(4-Ethoxy-3- 7.48 (m, 2H), 7.37 (m, 2H), 95.5methyl-biphenyl methyl-phenyl)- 7.24 (m, 2H), 6.88 (m, 1H), 4.09 (q,1,3,2-dioxaborolane J = 6.9 Hz, 2H), 2.41 (s, 3H), 2.32 (s, 3H), 1.47(t, J = 6.9 Hz) 4-Methoxy-3,4′-di- 2-(4-Methoxy-3- 7.48 (m, 2H), 7.42(m, 2H), 97 methyl-biphenyl methyl-phenyl)- 7.25 (m, 2H), 3.89 (s, 3H),2.42 (s, 1,3,2-dioxaborolane 3H), 2.33 (s, 3H)

The physical constants of all of the obtained products were, within thelimits of measurement accuracy, in good agreement with the respectiveparameters of the authentic product samples. The reaction mixturesalways remained lemon yellow, and no sign referring to an optionaldecomposition of the catalyst could be detected.

Example 8 Preparation of Stilbene Derivatives by Heck Coupling, Usingthe Catalyst of Formula (I)

Stilbene derivatives were prepared by reacting styrene with various arylbromides as shown in the following reaction scheme:

General Prescription:

552 mg (4 mmoles, 2 eq.) of K₂CO₃, 14 mg (0.25 mole % calculated for thearyl bromide substrate) of the catalyst of formula (I), 312 mg (0.343ml, 3 mmoles, 1.5 eq) of styrene, 2 mmoles (1 eq.) of the aryl bromidesubstrate and 10 ml of a 10:1 mixture of methanol and water were chargedinto an oven-dried Schlenk tube. The reaction was performed at 110° C.for 3 hours or 20 hours, as shown in Table 8. The conversions weredetermined by subjecting the reaction mixtures to GC, and the productwas then isolated. For tests Nos. 1, 2, 3 and 5 the productsprecipitated from the mixture upon cooling, thus they could be isolatedby a simple filtration; whereas for tests Nos. 4, 6 and 7 the productswere isolated by flash chromatography.

The results are summarized in Table 8.

TABLE 8 Test Aryl bromide Conversion, % Isolated No. A B C D E 3 hours20 hours yield, % 1 H F H H H 95 — 73 2 H H NO₂ H H 100 — 67 3 H H Me HH 100 — 93 4 OMe H OMe H H 57 78 60 5 H Me H Me H 98 — 96 6 Me H H H Me53 64 38 7 iPr H iPr H iPr 90 — 33

The NMR data of the resulting stilbene derivatives are as follows:

(E)-3-Fluorostilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.53 (d, J=7.5 Hz, 2H),7.39 (t, J=7.5 Hz, 2H), 7.41-7.22 (m, 4H), 7.11 (s, 1H), 7.10 (s, 1H),6.99-6.94 (m, 1H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 163.5 (C, d, J=244Hz), 139.9 (C, d, J=7.65 Hz), 137.1 (C), 130.3 (CH, d, J=8.18 Hz), 129.0(CH), 128.2 (CH), 127.7 (CH, d, J=2.70 Hz), 126.9 (CH), 122.7 (CH, d,J=2.78 Hz), 114.62 (CH, d, J=21.5 Hz), 113.0 (CH, d, J=21.5 Hz).

(E)-4-Nitrostilbene: ¹H NMR (300 MHz, CDCl₃) δ 8.23-8.21 (m, 2H), 7.63(d, J=8.7 Hz, 2H), 7.55 (d, J=7.5 Hz, 2H), 7.43-7.25 (m, 4H), 7.14 (d,J=16.5 Hz, 1H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 147.0 (C), 136.4 (C),133.6 (CH), 129.1 (CH), 127.3 (CH), 127.1 (CH), 126.5 (CH), 124.4 (CH).

(E)-4-Methylstilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.54 (d, J=7.8 Hz, 2H),7.46 (d, J=7.8 Hz, 2H), 7.41-7.36 (m, 2H), 7.31-7.26 (m, 1H), 7.21 (d,J=7.8 Hz, 2H), 7.12) s, 2H), 2.40 (s, 3H); ¹³C NMR (ATP) (75 MHz, CDCl₃)δ 137.8 (C), 137.8 (C), 134.8 (C), 129.7 ((CH), 128.9 (CH), 128.0 (CH),127.7 (CH), 126.7 (CH), 21.5 (CH₃).

(E)-2,4-Dimethoxystilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.53 (d, J=8.4 Hz,3H), 7.42 (d, J=16.5 Hz, 1H), 7.35 (t, J=7.5 Hz, 2H), 7.24 (dd, J=4.9Hz, 12.1 Hz, 1H), 7.02 (d, J=16.5 Hz, 1H), 6.53 (dd, J=2.2 Hz, 9.9 Hz,1H), 6.49 (d, J=2.4 Hz, 1H), 3.88 (s, 1H), 3.84 (s, 1H); ¹³C NMR (ATP)(75 MHz, CDCl₃) δ 160.5 (C), 138.3 (C), 128.5 (CH), 127.2 (CH), 127.0(CH), 126.9 (CH), 126.3 (CH), 123.3 (CH), 119.5 (C), 105.0 (CH), 98.5(CH), 55.5 (CH₃), 55.4 (CH₃).

(E)-3,5-Dimethylstilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.55-7.53 (m, 2H),7.41-7.36 (m, 2H), 7.31-7.26 (m, 1H), 7.18 (s, 2H), 7.11 (d, J=2.4 Hz,2H), 6.95 (s, 1H), 2.38 (s, 6H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 138.3(C), 137.5 (C), 129.7 (CH), 129.1 (CH), 128.9 (CH), 128.5 (CH), 127.7(CH), 126.7 (CH), 124.7 (CH), 21.5 (CH₃).

(E)-2,6-Dimethylstilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.54-7.52 (m, 2H),7.42-7.37 (m, 2H), 7.32-7.26 (m, 1H), 7.13 (d, J=16.8 Hz, 1H), 7.1 (m,3H), (m, 3H), 6.63 (d, J=16.8 Hz, 1H), 2.39 (s, 6H); ¹³C NMR (ATP) (75MHz, CDCl₃) δ 137.6 (C), 137.0 (C), 136.2 (C), 134.0 (CH), 128.7 (CH),127.9 (CH), 127.6 (CH), 126.9 (CH), 126.7 (CH), 126.3 (CH), 21.0 (CH₃).

(E)-2,4,6-Triisopropylstilbene: ¹H NMR (300 MHz, CDCl₃) δ 7.54-7.52 (m,2H), 7.43-7.38 (m, 2H), 7.33-7.26 (m, 1H), 7.22 (d, J=16.5 Hz, 1H), 7.07(s, 2H), 6.52 (d, J=16.8 Hz, 1H), 3.31 (h, J=6.9 Hz, 2H), 2.94 (h, J=6.9Hz, 1H), 1.33-1.23 (m, 18H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 142.4 (C),141.4 (C), 132.3 (C), 128.6 (CH), 127.7 (C), 123.4 (CH), 122.1 (CH),121.7 (CH), 121.0 (CH), 115.3 (CH), 29.0 (CH), 24.9 (CH), 18.7 (CH₃),18.5 (CH₃).

Example 9 Preparation of Phenylacetylene Derivatives by SonogisharaCoupling, Using the Catalyst of Formula (I)

Phenylacetylene derivatives were prepared by reacting phenylacetylenewith various aryl bromides as shown in the following reaction scheme:

General Prescription:

276 mg (2 mmoles, 1 eq.) of K₂CO₃, 7 mg (0.25 mole % calculated for thearyl bromide substrate) of the catalyst of formula (I), 0.165 ml (1.5mmoles, 1.5 eq) of phenylacetylene, 1 mmoles (1 eq.) of the aryl bromidesubstrate and 5 ml of the solvent [solvent (a): a 5:1 mixture ofmethanol and water; solvent (b): n-butanol; solvent (c):glycerol-formal] were charged into an oven-dried Schlenk tube. Thereaction was performed at 110° C. for 3 hours or 24 hours, as shown inTable 9. The amounts of the products were determined by subjecting thereaction mixture to GC.

The results are summarized in Table 9.

TABLE 9 Test Aryl bromide After 3 hours After 24 hours No. A B C DSolvent Conv. % Product % Conv. % Product % 1 H OMe Me H (a) 47 43 71 572 H NO₂ H H (a) 88 43 100 56 3 H CH₃ H H (a) 51 48 81 78 4 iPr iPr H iPr(a) 10 8 97 46 5 H OMe Me H (b) 91 65 100 66 6 H NO₂ H H (b) 100 78 — —7 H Me H H (b) 100 84 — — 8 iPr iPr H iPr (c) 36 31 100 87

The NMR data of the resulting phenylacetylene derivatives are asfollows:

1-Methyl-4-(phenylethynyl)-benzene: ¹H NMR (300 MHz, CDCl₃) δ 7.43 (d,J=8.0 Hz, 2H), 7.26-7.22 (m, 5H), 6.70 (d, J=8.3 Hz, 1H), 3.75 (s, 3H),2.13 (s, 3H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 158.2 (C), 133.9 (CH),131.5 (CH), 130.6 (CH), 128.5 (CH), 128.3 (CH), 127.9 (CH), 123.8 (C),109.9 (CH), 89.9 (C), 55.4 (CH), 16.1 (CH).

1-Nitro-4-(phenylethynyl)-benzene: ¹H NMR (300 MHz, CDCl₃) δ 8.17 (d,J=9.0 Hz, 2H), 7.62 (d, J=9.0 Hz, 2H), 7.58-7.55 (m, 2H), 7.41-7.38 (m,3H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 147.0 (C), 132.3 (CH), 131.9 (CH),130.3 (C), 129.4 (CH), 129.0 (CH), 123.7 (CH), 122.2 (C), 94.8 (C), 87.7(C).

1-Methyl-4-(phenylethynyl)-benzene: ¹H NMR (300 MHz, CDCl₃) δ 7.60-7.57(m, 2H), 7.49 (d, J=8.1 Hz, 2H), 7.40-7.35 (m, 3H), 7.20 (d, J=7.9 Hz,2H), 2.41 (s, 3H); ¹³C NMR (ATP) (75 MHz, CDCl₃) δ 138.6 (C), 131.8(CH), 131.7 (CH), 129.3 (CH), 128.5 (CH), 128.3 (CH), 123.7 (C), 120.4(C), 89.8 (C), 89.0 (CH), 21.7 (CH₃).

Phenyl-(2,4,6-triisopropyl-phenyl)-acetylene: ¹H NMR (300 MHz, CDCl₃) δ7.58 (dd, J=8.0 Hz, 1.4 Hz, 2H), 7.43-7.35 (m, 3H), 7.07 (s, 2H), 3.65(sept, J=6.9 Hz, 2H), 2.96 (sept, J=6.9 Hz, 1H), 1.36 (d, J=6.9 Hz,12H), 1.32 (d, J=6.9 Hz, 6H);

¹³C NMR (ATP) (75 MHz, CDCl₃) δ 150.9 (C), 149.5 (C), 131.5 (CH), 128.6(CH), 128.1 (CH), 124.6 (CH), 120.7 (CH), 118.7 (C), 97.0 (C), 87.3 (C),4.9 (CH₃), 32.2 (CH₃), 24.2 (CH₃), 23.6 (CH₃).

The above reaction was repeated by using 2-bromo-3-methyl-but-2-ene assubstrate. The obtained results are listed in Table 10.

TABLE 10 After 3 hours After 24 hours Test Conversion, Conversion, No.Solvent % Product, % % Product, % 1 (a) 22 10 64 40 2 (b) 24 15 84 28 3(c) 93 87 100 94

The NMR data of the resulting product are as follows: ¹H NMR (300 MHz,CDCl₃) δ 7.45-7.39 (m, 2H), 7.34-7.22 (m, 3H), 2.02 (s, 3H), 1.89 (s,3H), 1.79 (s, 3H).

Example 10 Preparation of N-Phenyl-Piperidine by Buchwald Reaction,Using the Compound of Formula (I) as Catalyst

-   -   -   -   -   224 mg (2 mmoles) of potassium tert.-butoxide, 70 mg                    (2.5 mole % calculated for the bromobenzene                    substrate) of the catalyst of formula (I), 105 μl (1                    mmole) of bromobenzene, 198 μl (2 mmoles) of                    piperidine and 5 ml of solvent were charged into an                    oven-dried Schlenk tube. The reaction mixture was                    heated on an oil bath at 110° C. for 24 hours,                    allowed then to cool to room temperature, and                    evaporated under reduced pressure. The residue was                    purified by column chromatography on silica gel                    (eluant: hexane/ethyl acetate) to give the desired                    product; ¹H NMR (300 MHz, CDCl₃) δ 7.31-7.26 (m,                    2H), 7.00-6.97 (m, 2H), 6.89-6.84 (m, 1H), 3.19 (t,                    J=5.6 Hz, 4H), 1.79-1.72 (m, 4H), 1.64-1.59 (m, 2H).

The results of the tests performed in different solvents are summarizedin Table 11.

TABLE 11 Test Conversion, % No. Solvent after 3 hours after 24 hours 1toluene 40 47 2 DMSO 35 37

What we claim is:
 1. A composition comprising apalladium(0)-tris{tri-[3,5-bis(trifluoromethyl)-phenyl]-phosphine}complex of formula (I)


2. The composition of claim 1 in a solid form.
 3. The composition ofclaim 1 having a melting point of 220° C. as determined by DSC in inertatmosphere.
 4. The composition of claim 1, having a decomposition pointof 169.5° C. as determined by DSC in air under atmospheric pressure. 5.A palladium(0) complex comprising three fluorinated phosphine compounds.6. The palladium(0) complex of claim 5 exhibiting a stabilitycharacterized by no measurable decomposition on the basis of ³¹P, ¹⁹F,¹³C and ¹H NMR spectra following 4 months of storage in air at atemperature of 25° C.
 7. The palladium(0) complex of claim 5 exhibitinga stability characterized by no measurable decomposition on the basis of³¹P, ¹⁹F, ¹³C and ¹H NMR spectra following 20 months of storage in airat room temperature.
 8. The palladium(0) complex of claim 5 having amelting point in inert atmosphere of 220° C.
 9. The palladium(0) complexof claim 5 exhibiting stability at any temperature below its meltingpoint.
 10. The palladium(0) complex of claim 5 exhibiting insolubilityin water at industrially relevant temperatures and stability when storedin water.
 11. The palladium(0) complex of claim 5 comprising a yellowsolid.
 12. The palladium(0) complex of claim 5 that dissolves at around90° C. in aqueous alcohols.
 13. The palladium(0) complex of claim 5having catalytic activity in cross coupling reactions at a concentrationof from 0.1 to 0.3 mole % of the substrate.
 14. A method for catalysinga C—C, C-heteroatom, or hydrogenation reaction comprising carrying outthe C—C, C-heteroatom or hydrogenation reaction in the presence of thepalladium(0) complex of claim
 5. 15. The method of claim 14, wherein thereaction is a C—C cross-coupling reaction.
 16. The method of claim 14,wherein the C—C cross-coupling reaction is selected from the groupconsisting of: Suzuki coupling, Heck coupling and Sonogashira coupling.17. The method of claim 14, wherein the amount of palladium(0) complexused in the reaction for 1 mole of substrate is 0.25 mole % or less. 18.The method of claim 14, wherein the reaction is a C—N coupling reaction.19. The method of claim 18, wherein the reaction is a Buchwald coupling.